Purification of hydrogen haldes



'life of the metal halide.

Patented Nov, 20,1 1941i rUalFrcA'rIoN assess: o F HYDROGEN HALml-:s

Herman Pines and Herman S. Bloch, Riverside, Ill., asslgnors to Universal Oil Products Company, Chicago, llll., a corporation of lDelaware.

Application December 31, 1943, Serial No. 516,434

v 1 2 Claims. (01.'23-,150

This application is afcontmuation-m-prt ,of application Serial No. 455,509,'nled August 20,

1 1942, which is a continuation-impartof application Serial No. 360,906, filed October 12, 1940, now Y* U. s. Patent 2,300,23 l

IThis invention relates to the removal of undesirable impurities in hydrogen halides and Ais more specifically concerned. with4 the removal of impurities such as carbon monoxide, carbon dioxide,

hydrogen sulfide, etc., which may be present in= varying amounts as contaminants in commerc'ially prepared hydrogen lides including hydrogen chloride, hydrogen romide, hydrogen nuoride andhydrogen iodide.

Up-'to the advent of commercial processes using' `metal halide catalyst of the Friedel-Crafts type, and particularly aluminum chloride catalyst in conjunction ,with hydrogen chloride, for vsuch processes as isomerization of saturated hydrocarbons and alkylation of lsoparafilnic by olenic 1 hydrocarbons, there had been little commercial demand' for substantially anhydrous hydrogenliquid phase.

Y ful impurities will usually not be over 5%. The

harmful impurities are those containing oxygen, sulfur or the like, such as oxygen; carbon monoxide, carbon dioxide, hydrogen sulilde, etc. Hy-

drogen and Vnitrogen are usually not harmful to metal halide catalysts andthe only objection to their presence is that of a diiuent effect.

In a broad aspect the present invention relates to a' processior purifying hydrogen halides which' comprises separating a gaseous phase and a. liquid phase, reacting the gaseous phase with an organic compound in the presence of a metal halide catalyst of the Friedel-Crafts type to convert at least a portion of the impurities and to leave .a

puried hydrogen halide fraction, and blending the purified. hydrogen halide fraction with said In one specic embodiment the present inventionrelates to a process for purifying a hydrogen chloride fraction containing up to impurities which Jcomprises partially liquefying said fraction to form a liquid phase and a gaseous chloride, and this demand had been met by dryf ing the hydrogen chloride produced'in the wellknown salt cake process infwhich ordinary sodium chloride was treated with sulphuric acid,

generally in. two stages, although this process was more .commonly used to* produce hydrochloric acid. As`\the. demand for anhydrous hydrogen chloride has increased, other processes have been developed in which hydrogen chloride is Amanufactured by the' action of chlorine on water gas mixtures consisting of hydrogen and carbon monoxide. These processes may utilize s pecic catalysts and light. under controlled conditions to facilitate the union of hydrogen and chlorine to produce the desired hydrogen chloride. While some of the mixtures thus obtained are partially puried before sale in order to remove a maior portion ofthe impurities. a considerable amount of the marketed hydrogen chloride still contains phase, the gaseous phase comprising '15% or less of said fraction, reacting. the gaseous phase with a saturated hydrocarbon in the presence of an aluminum chloride catalyst to produce oxygenated hydrocarbons and to leave a puried hydrogen chloride fraction, and blending the pure hydrogen chloride fraction with said liquidphase.

In accordance with the present invention an impure hydrogen chloride fraction is treated by a combination of interdependent and mutually related steps to remove harmful contaminants and to thereby` produce a hydrogen chloride iraction of Vhigh purity.

In the first step of the process a gaseous phase comprising not more than 15% of said hydrogen upto 10% of impurities of th'e type heretofore indicated so that when they are, used in connec' tion with metal halide catalysts the cause def.

inite deterioration with shorteningo .the active chloride fraction is separated from a liquid phase.

We have foundthat by removing this comparatively small proporton as a gaseous phase, the residual liquid phase will contain an unexpectedly.

low percent of contaminants. `In some cases 'satisfactory purification may be accomplished by removing less than 10% .and even 5% or less,

The present invention 'is' directedto the fllrA I' ther purincation ofthe partially purined hydro- Sen chloride fraction ,in order to decrease the impurities which,` as heretofore set forth, may range 11D t0 10%. to a considerably lower percentage so that the hydrogen chloride fraction may be used in connection with metalhalide catalysts without excessive deterioration thereof. Although the total impurities may range up to '410%,the harm@ .depending upon th'e amount and character` of the impurities present therein.`

In the second step 'of the process, the thus separated gaseous phase is reactedwith an Vo1"- ganiccompound and particularly with a saturated hydrocarbon in the 'presence ofza metal.

halide catalyst of the FriedelfCrafts type and particularly aluminum chloride under conditions to react the oxygenfcontaining impurities with the hydrocarbon., The reaction products of the vimpurities andhydrocarbon will usually be reand thus are readily separated from the hydrogen chloride and excess hydrocarbons.

In the third stepof the process, separation of excess saturated hydrocarbon from hydrogen chloride may be accomplished by any suitable method such as-by fractional distillation in case the saturated hydrocarbon is` of suill'ciently different boiling range from hydrogen chloride to permit their ready separation, or by selective adsorption of the hydrogen chloride on a suitable adsorbent, followed by desorption 'ofthe puried hydrogen chloride.

In the final step of the process, the purified hydrogen chloride, separated either by fractional distillation, selective adsorption. Vor otherwise is blended with the originally separated liquid phaseA to thereby produce a final hydrogen chloride fraction of high purity.

The invention will be further explained in connection with the attached diagrammatic now drawing. Figure I illustrates one specific embodiment of the invention in which the purified gaseous hydrogen chloride fraction is separated by fractional distillation, while ,Figure II illustrates a. similar process in which the separation. of the puried gaseous hydrogen chloride frac` f desired in the'iinal product. Zone 6 is provided in the lower portion thereof with any suitable heating means, such as internal heating coils 1, through which steanror other suitable heating medium is introducedl through line 8 containing valve 9 and is withdrawn therefrom through line I containing valve Il. heating coils 1 may be omitted when desired.

. and also that any other suitable form of heating may be employed. When desired, suitable cooling means may -be employed in the upper portion of vzone 6 and this is illustrated by line ^I2 containing valve I3, although it is understood that other suitable cooling means may be utilized.

'Ihe function of element 3 and zone -8 isto separate a gaseous phase comprising not more than 15% of the impure hydrogen chloride fraction charged to the process. The remaining liquid Itis understood that vsaturated hydrocarbon is introduced to theI process through line 25 and valve 26 into line 23. wherein it is admixed with the gaseous hydrogen chloride phase and then directed into reaction zone 21.

The organic compound introduced through line 2-5 may be an alcohol, ether etc., but preferably is a saturated hydrocarbon and particularly a parailinic'hydrocarbon. We have found that a saturated hydrocarbon readily reacts with the impurities under the conditions hereinafter specied. Propane, butane, pentanes and hexanes are .duced continuously or intermittently to zone. 21

by way of line 23 containing valve 2-4. The temperatures employedin zone 21 are substantially atmospheric, although subatmospheric temperatures as low as 25 C. and super atmospheric temperatures up to about 350 C. may be 'employed. Although atmospheric pressure may be employed, it is usually preferred to utilize superatmosph'eric pressure which `rmay range u'p to 400 pounds or more.

Thecatalyst and reaction products of the im- -purities and hydrocarbon will be liquid, senil-y solid. or solid and will be retained in the aluminum chloride catalyst phase-when liquid or semi-solid. The catalyst phase Acontaining the aforementioned-'reaction products may be continuously or intermittently removed from 'zone 21 through line 25' and-svalve 26. The oxygenated hydrocarbonsA formed in zone 2'1 may be recovered from the fraction will now contain an unexpectedly low,l

percentage of contaminants and may be withdrawn from zone 6 through line I4, While a portion thereof may be removed from the process through valve I5, in accordance with the present invention, at least a portion of the liquid phase is directed through line I6 and valve I1 for blending in the manner to be vhereinafter described in detail.

The gaseous phase separated in zone 6, which will contain a large proportion of the contaminants, is withdrawn through line I8 and, al-

thoug'h a portion thereof may be removed from 'through line 34 and valve 35.

catalyst `by hydrolysis or by any other suitable method. The thus recovered oxygenated hydrocarbons are suitable for many uses. The hydrogen chloride and excess saturated hydrocarbon are directed from zone 21fthrough line' -281and valve 29 into separation zone 30.'

In the embodiment ofthe invention illustrated in Figure I, the excess hydrocarbon is separated valve 31 to the upper portion of zone 30.- In case the overhead fraction withdrawn from zone 30 is subjected to condensation, a particularly suitable cooling medium for this purpose comprises a por' tion of the condensate. The excess hydrocarbon is withdrawn from zone 30 through line 38 containing valve 39.

Hydrogen chloride is withdrawn from the upper portion of zone 30 through line 40 and, a portion thereof may be removed from the process through valve 4I but, in accordance with the present invention, at least a portion of the purified hydrogen chloride is directed through line 42 and valve 1 v 2,389,467 I3 to be blended with the previously separated liquid fraction inline I6. Figure 1I ofv thedrawing illustrates a process in which the hydrogen chloride is separated from the excess vsaturated. hydrocarbon by means o! selective adsorption. Intheinterest of simplicity zone 6, communicating lines, compressors, etc., havebeen omitted since they are the sameas illustrated in Figure I. Reaction zone 2 corresponds to reaction zone v'il in Figure I.- The hydrogen chloride and excess hydrocarbons are directed through line 28 containing valve 28 'into adsorption zone 30'. Although one adsorption coiuinn is uiustratedin the drawing, it 1s understood that two ormore of such zones may be unduly limiting the broad scope of the invention.

employed so thatthe process may be continuous;

that is, one column being utilized to adsorb hydrogen chloride, while the hydrogen chloride in f the other column is being recovered.

Zone 30 is packed-with a suitable granular solid adsorbent such as dry charcoal of either animal or vegetable origin, similar activated chars derived from petroleum coke, activated alumina,

'silica gel, diatomaceous earth, or any active and inzone 21. i

The' hydrogen chloride is selectively adsorbed by the adsorbent in zone 30', while the excess hydrocarbons pass therethrough and are removed from 30' through line 38' containing valve 39'.

After the adsorption of hydrogen chloride in one adsorption column has progressed to the de- A cylinder oi' commercial hydrogenv chloride atroom temperature was of the following composition:

` Gaseous Liquid M91 percent phase phase Hydrogen chloride 83.6 98.3

0.5,' 0.09 2.2 0.09 y10.1 1.11 Carbon monoxide 3.0 0.37

A gaseous phase, comprising aboutl of the total hydrogen chloride fraction, was separated and the compositionof the remaining-gaseous phase and liquid phase were as follows:

Gaseous Liquid Mol percent phase phase Hydrogen chloride 86. 2 99. 2 Oxygen 0.4 0.05 H drogen. 1.5 0.04 N trogen, 9. 2 0.53 Carbon monoxide. -2. 7 0. 19

HIt is to be noted that when as little as 5% is removed as a gaseous phase, the remaining liquid phase is of a markedly high purity.

The gaseous phase may be reacted with normal butane at a temperature of 100 C. in the presence of an aluminum chloride catalyst. The reaction products may then be subjected to fractional distillation to` separate a puried hydrogen chloride fraction which is then blended with'the heretofore separated liquid phase to produce a ilnal hydrogen chloride fraction of high purity.

A major feature of the present process is that 7 .only a comparatively small amount of the. hydrosired extent; the ow of products to and from the column is switched to a second adsorption column. The hydrogen chloride may be recovered from the first adsorption column by desorption in any suitable manner. This may comprise raising the temperature, by suitable means not illustinted, and/o1" reducing the pressure in the ad` sorption column by means of valve 29 in'order to liberate the hydrogen chloride.

. The desorption temperature may range from about 40 to about 260 C. or more, and the presi sure may be reduced to atmospheric or below, but not generally below 0.1 atmosphere.' The desorbed hydrogen chloride may be rembved from the upper portion of zonell' through line '.0' and, while afportion thereof may be withdrawn -from the process through valve 4I', in accordance with the present invention, at least a portion thereof is directed through line 42' and valve 4,3' to commingle with the previously separated liquid fraction in line I6 as illustrated in Figure I.

It is also within the scope of the invention to remove the hydrogen halide from the adsorbent by stripping with a suitable stripping medium. However, this type of operation is generallynot it. 'One such reason may be the preparation of a hydrogen chloride-isobutane fraction for use in an alkylation process and, in this case, isobutane may be used to strip the hydrogen chloride from` the adsorbent. Y Y

- I'he invention is further illustrated'in the following example but not with the intention' of 7'5'phase comprising lnot more than 15% oi' said preferred unless there is a special reason for using gen chloride fraction need be treated in order to obtain a final productiof high purity. The importance of this advantage is readily seen in the reduced size and therefore costs of equipment in the treating and separating steps of the process.

We claim as our invention: n j

l. A process for purifying an impure hydrogen halide fraction containing a gaseous impurity of the group consisting of carbon oxides and hydrogen suljde, which comprises partially liquefying said fraction to separate the same into a gaseous phase and allquid phase, reacting theAgaseousv phase with an organic compound in the presence of a metal halide catalyst. of the Friedel-Crafts type, and recovering from the resulting products .a purie'd hydrogen halide fraction.

2. A process for purifying an impure hydrogen halide fraction containing a gaseous impurity of the group consisting of carbon oxides and hydrogen sulilde, which comprises partially liquefying said fraction to separate the `sameinto a gaseous phase and a liquid phase, contacting said gaseous phase and an organic compound with a metal halide catalystv of the Friedel-Crafts type under conversionA conditions to react atleast a portion of the impurities with said organic compound,

separating from the resulting products a puried hydrogen halide fraction, and blending thepurined hydrogen Vhalide fraction with said liquid phase tp lform a of high purity. A

l3. A process for'purifying a hydrogen chloride fraction containing not more than 10% carbon oxide impurities, which comprises partially liqueflnal hydrogen halide fraction fying said fractin tol separate lthe same into a gaseous phase-and a liquidphase, the gaseous ized in that said puried hydrogen halide is separated by selective adsorption o n a solid adsorbent and then is recovered by desorption.

6. A process for ,removing carbon oxide impurities from ashydrogen chloride fraction consaid fraction to4 condense at least 85% of said fraction and to leave uncondensed not more than 15% of said fraction. withdrawing said un- Vcondensed portion and reacting the same with a densed portion with said parafllnlc hydrocarbon,

contacting the resultant products with a suitable adsorbent `under conditions to selectively adsorb the hydrogen chloride and to thereby separate it l from excess paralnic hydrocarbon, subsequently recovering the hydrogen chloride from the-adsorbent by desorption thereof, and blending the thus recovered hydrogen chloride with the conldensed portion of said fraction.

taining the same, which comprises partially liquei fying said fraction to separate the same into a gaseous phase anda liquid phase, thegaseoussultant product to separate a puried hydrogenl chloride fraction and blending the puriiled hydrogen chloride fraction with said liquid phase.

7. -A process for removing carbon oxide impuri.. ties from a hydrogen chloride fraction containing the same, which comprises partially liquefying said fraction to condense atleast 85% of said fraction and to leave uncondensd not more than 15% of said fraction, withdrawing said uncondensed portion and reacting the same with a parailinic hydrocarbon in the presence of an aluminum chloride catalyst under conversion conditions to react the impurities contained in said uncondensed portion with said paraiim'c hydrocarbon, fractionating the resultant products to separate a purified hydrogen chloride fraction,

and blending the purled hydrogen chloride frac.

tion with the condensed portion of said fraction.

8. A process for removing carbon oxide impuri.

ties from a hydrogen chloride fraction containing 9.` A process for purifying a hydrogen halide gas containing a carbon oxide impurity, which comprises liquefying the major portion of said gas and separating the remaining gaseous phase from the liquid phase, contacting said gaseous phase with an organic compound and a metal halide catalyst ofthe Friedel-Crafts type under reaction conditions t'o react at least a. portion of thecarbon oxide impurity with said organic compound, and separating purifiedliydrogen halide fro the resultant reaction products.

1 A process for purifying a hydrogen chloride gas containing a carbon oxide impurity, which comprises liquefying the major portion of said gas and separating the remaining gaseous phase from the liquid phase, contacting said gaseous phase with an organic compound and aluminum chloride under reaction conditions to react at least a portion of the carbon oxide impurity with said organic compound, and separating purilled hydrogen chloride from the resultant reaction products. i

l11. The process as defined in claim. 9 further chararerized in that said organic compound is a paraillnic hydrocarbon.

12. 'Ihe process as defined in claim 10 further characterized in that said organicv compound is a paraillnic hydrocarbon.

, HERMAN FINES.

HERMAN S. BLOCH. 

